Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
  • C08F212/22—Oxygen
  • C08F212/24—Phenols or alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/78—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/20—Metallic substrate based on light metals
  • B05D2202/25—Metallic substrate based on light metals based on Al

Definitions

• the instant invention relates to the field of the treatment of surfaces based on metal, and especially metal surfaces intended to be coated with film-forming organic compositions such as paints, varnishes or adhesive compositions.
• the invention is more especially directed to a treatment of said metal surfaces aiming at providing a protection especially against corrosion and/or an enhancement of the adherence of the film-forming organic.
• conversion coating refers to a layer formed on the surface of a metal, that is an advantageous replacement of native oxide on said surface (especially on aluminum), and which is obtained by the controlled chemical formation of a film on the metallic surface by reaction with chemical elements of the metallic surface, so that at least some of the cations dissolved from the metallic material are deposited in the conversion coating.
• coating such as conversion coatings are obtained by reacting the metal surface with solutions containing metal cation and fluorides.
• chromium-containing coatings have been proposed (typically obtained by reaction of the surface with a solution including H 2 CrF 6 ), and, more recently, less toxic coatings based e.g. on zirconium, titanium or other metals (for example obtained by reaction of the surface with a solution including H 2 TiF 6 , H 2 ZrF 6 , H 2 HfF 6 , H 2 AlF 6 , H 2 SiF 6 , H 2 GeF 6 , H 2 SNF 4 , or HBF 4 ).
• a conversion coating may include other compounds such as silane precursors for example.
• a typical additive is ACUMERTM 1510 available from DOW (and previously form Rohm & Haas) that has been widely described for this kind of application.
• ACUMERTM 1510 available from DOW (and previously form Rohm & Haas) that has been widely described for this kind of application.
• it may be especially be refered to WO97/13588 , US 4,191,596 , or US4921552 .
• One aim of the present invention is to provide a new method for treating a metal surface, that imparts a good protection of the metal surface against corrosion and a good adherence of film-forming organic compositions such as paints, varnishes or adhesive compositions applied to the metal surface.
• the instant invention proposes to make use of a specific polymer, preferably together with (namely before, during, or after) the formation of a conversion coating, which advantageously leads to treated metal surface that reveals very interesting: when coated by a film-forming compositions such as a paint, varnish or adhesive composition, a good adherence is obtained between the surface and the coated composition. Besides, a good protection of the surface is obtained, especially against corrosion.
• a film-forming compositions such as a paint, varnish or adhesive composition
• the instant invention make use of at least one Polymer P, which is a polymer obtained by radical copolymerization of a mixture of:
• the polymer P typically contains a mixture of the two isomers as the allylcatechol, having typically a molar ratio 4-allylbenzene-1,2-diol to 3-allylbezene-1,2-diol between 30/70 and 70/30, for example between 50/50 and 70/30.
• the polymer P preferably contains acrylic acid (AA) at a content of 10 to 90% in mol; methacrylic acid (MAA) at a content of 1 to 70% in mol, and allylcatechol at a content of 1 to 20% in mol, each of the molar ratio being calculated on the basis of the total quantity of AA, MAA and allylcatechol.
• AA acrylic acid
• MAA methacrylic acid
• allylcatechol at a content of 1 to 20% in mol
• the molecular weight of polymer P is typically between 10 and 150 kDa., e.g. between 15 and 100 kDa.
• the polymer P contains allylcatechol at a content of 1 to 5% mol.
• the polymer P generally contains MAA at a content of at most 70% mol and has a molecular weight M w of 80 kDa or less.
• the polymer P contains allylcatechol at a content of 5 to10 % mol. mol.
• the polymer P generally contains MAA at a content of at most 40% mol and has a molecular weight M w of 40 kDa or less.
• the polymer P contains allylcatechol at a content of 10 to 15% mol.
• the polymer P generally contains MAA at a content of at most 20% mol and has a molecular weight M w of 30 kDa or less.
• the polymer P contains allylcatechol at a content of 15 to 20% mol.
• the polymer P generally contains MAA at a content of at most 10% mol and has a molecular weight M w of 20 kDa or less.
• the polymers P as described above that have not been described in the prior art at the inventors best knowledge, constitute a subject-matter of the invention.
• one specific object of the instant invention is the use of at least one polymer P as defined above for treating a metallic surface intended to be coated by a paint, a varnish or an adhesive.
• the metal surface to be treated is preferably a surface comprising a metal selected from aluminum, steel, zinc, magnesium and their alloys.
• the invention is especially interesting for metal surface of aluminum or aluminum alloy.
• a conversion coating is applied on the metallic surface to be treated, by reaction of said surface with a conversion composition (in other words, a conversion composition a is applied on the metallic surface for forming a conversion coating thereon).
• a conversion composition a is applied on the metallic surface for forming a conversion coating thereon.
• all or part of the polymer P is present in a paint, a varnish or a coating applied on the surface, preferably after application of a conversion coating on the metal surface.
• one other specific object of the invention is a process for coating a metallic surface with a paint, a varnish or an adhesive, preferably with a paint, including a step of treating said surface with at least one composition including at least one polymer P as defined above.
• the composition comprising the polymer P may typically be:
• the conversion composition including a polymer P and the paint, varnish or adhesive compositions containing the same also constitute specific object of the instant invention
• the polymer P is present in the conversion composition and/or in a solution or dispersion applied on a conversion coating.
• the paint, varnish or adhesive is applied on a surface previously treated by the polymer.
• an additional layer may applied between the treated surface and the paint, varnish or adhesive is applied (this is for example the case for the treatment of metal foil on a first site, that have then to be coated, for example painted, on a second site: in that case, a lubricant may be applied on the treated foil, in order to allow to roll the foil and ease its transportation).
• a specific object of the instant invention are the materials comprising a metal surface comprising a metal surface which is in all or part (i) treated with a polymer P as defined above and (ii) covered by a paint, a varnish or an adhesive.
• These materials include i.a. materials that have a metal surface in all or part covered by:
• Any metal surface may be treated with polymer P of the invention, but the invention is especially suitable for treating metal surfaces of:
• the invention is especially interesting for metal surface of aluminum and aluminum alloys, such as Aluminum Alloy AA 5005 tested in the appended examples, or other alloys such as those of Series 1xxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx, such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182.
• Aluminum Alloy AA 5005 tested in the appended examples or other alloys such as those of Series 1xxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx, such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182.
• a conversion coating When a conversion coating is applied on the metal surface to be treated according to the invention, it may be obtained by contacting the surface with any conversion composition known from the prior art.
• Contacting the metal surface with the conversion composition may be made by any means known per se, such as dip coating in a conversion bath or spray coating, as illustrative examples.
• the conversion composition used according to the invention may typically contain fluorides anions and cationic metals, e.g. compounds such as H 2 CrF 6 , or more preferably chromium free compounds such as H 2 TiF 6 , H 2 ZrF 6 , H 2 HfF 6 , H 2 AlF 6 , H 2 SiF 6 , H 2 GeF 6 , H 2 SNF 4 , or HBF 4 .
• fluorides anions and cationic metals e.g. compounds such as H 2 CrF 6 , or more preferably chromium free compounds such as H 2 TiF 6 , H 2 ZrF 6 , H 2 HfF 6 , H 2 AlF 6 , H 2 SiF 6 , H 2 GeF 6 , H 2 SNF 4 , or HBF 4 .
• the conversion composition may also include other compounds, such as silane precursors for example, and/or cerium salts, and/or terbium molybdate.
• the conversion composition may contain all or part of the polymer P used according to the invention for treating the surface. In that case, the application of the conversion layer lads per se to a surface treatment according to the invention.
• the treatment is typically obtained after the formation of the conversion layer, by contacting the metal surface carrying the conversion layer with the polymers P (they may typically be applied on the conversion layer in the form of a solution or a suspension of polymers P, or within a paint, a varnish or an adhesive composition applied on the conversion layer).
• the polymer P both in the conversion composition and within a paint, a paint, a varnish or an adhesive composition applied on the conversion layer.
• a polymer P1 was prepared as follows: 4-allylpyrocatechol (5.50 g, 36.6 mmol) having a molar ratio 4-allylbenzene-1,2-diol and 3-allylbenzene-1,2-diol of 60/40, acrylic acid (AA) at 58.4% in water (1.47 g, 11.9 mmol) and 2,2'-Azobis(2-methylpropionamidine)dihydrochloride (V-50) at 5% in water (74.49 g, 13.7 mmol) were added in a 500 mL three-neck round-bottom flask. After stirring for 20 minutes under nitrogen, the round-bottom flask was placed into a 66°C oil bath.
• Tests have been performed on aluminum alloy panels (AA5005, from Q-Panel), with usual lab equipment (beakers, oven, ...), a powder coating installation (GEMA 2C from Industrie Systemes) and a corrosion chamber (Q-FOG CRH 600L, from QFOG).
• each pannel to be tested in a combined cleaning-etching bath which was a 1L bath is typically made by diluting a commercially available formulation, DBT ALU 200, available from Chemtec Aertec (5g of DBT ALU 200 into 995g of water).
• the pannel was dipped in the cleaning-etching bath for 3min under light stirring (200rpm) at 50°C. The pannel was then rinsed with 1L of de-ionized water.
• Each panel was then painted with a polyester white powder paint from RIPOL (BIANCO RAL 9010).
• the polymer of the invention is clearly better than the comparative, even after 1000h.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Emergency Medicine (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Chemical Treatment Of Metals (AREA)

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• 2018
  • 2018-11-27 EP EP18208625.6A patent/EP3659716A1/de not_active Ceased
• 2019
  • 2019-11-27 WO PCT/EP2019/082792 patent/WO2020109413A1/en unknown
  • 2019-11-27 EP EP19809837.8A patent/EP3887068B1/de active Active
  • 2019-11-27 CN CN201980074620.0A patent/CN113015582B/zh active Active
  • 2019-11-27 BR BR112021006893-7A patent/BR112021006893A2/pt not_active Application Discontinuation
  • 2019-11-27 US US17/293,543 patent/US20220002456A1/en active Pending

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